Method of manufacturing a moulded mineral wool product and a product of such kind

ABSTRACT

The present invention concerns a method of producing a moulded mineral wool insulation product, said method comprising the steps of providing a mixture by mixing mineral fibres with a binder composition, and providing said mixture in a mould form, and then curing the binder, wherein the binder composition comprises at least one hydrocolloid, and then removing the moulded product from the mould form.

REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national stage application ofPCT/EP2017/079088, filed Nov. 13, 2017, which claims priority toPCT/EP2017/061418 and PCT/EP2017/061419, both filed May 11, 2017. Theentire content of each application is incorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure relates to a method of manufacturing a mouldedmineral wool product and a product of such kind.

BACKGROUND OF THE INVENTION

Moulded mineral wool products are known, e.g. from EP 1 897 862 A1. Itis thus known to supply thermal insulation elements in various shapes,such as cuboid batts, boards or slabs, cylindrical pipe sections forpipe insulation and pre-shaped elements for pipe-elbows, valves, etc.Such moulded fibrous products may also be produced for use in thevehicle industry, such as sound and/or thermal insulation components inautomobiles, trucks, busses, trains and other ground vehicles. Anotherexample of light-weight thermal insulation components for the automotiveindustry is also known from US 2014/0238648. Typical applications ofsuch moulded composite products is linings and fitting elements of carinteriors, such as self-supporting linings for the cabin, the cabinroof, the door panels, trim panels, instrument panels, etc.

Although different kinds of materials are used for such components, theuse of mineral wool fibres is attractive due to its good propertiesregarding thermal insulation and fire resistance. However, productioncosts may be an issue due to the production process just as it isdesirable and in the automotive industry and other industries it is arequirement that the materials used are non-toxic, which could be anissue when using mineral wool fibre materials, but as explained in EP 1897 862 A1 it is found possible to avoid the use of potentially toxiccompounds, such as phenol and formaldehyde, in the binder system.

In the conventional production of moulded mineral fibre products, thebinder must be cured while the material is being shaped in the mould.This curing is achieved by heating the product, typically to atemperature of 200-250° C. for a certain amount of time and often byblowing hot air through the product. This heating adds to the productiontime and the production costs just as it sets some constrains in whichmaterials can be used since the materials must be capable ofwithstanding this elevated heating.

SUMMARY OF THE INVENTION

With reference to the above it is an object to provide a moulded mineralwool product with a binder that does not need an elevated temperaturefor curing.

Accordingly, by the present disclosure it is realised that a mouldedmineral wool product may be produced using a binder compositioncomprising at least one hydrocolloid. These types of binder compositionshave the advantage that they can be cured at relatively lowtemperatures.

Accordingly, by the disclosure there is provided a method of producing amoulded mineral wool insulation product, said method comprising thesteps of:

-   -   providing a mixture by mixing mineral fibres with a binder        composition, and    -   providing said mixture in a mould form, and then    -   curing the binder composition, wherein the binder composition        comprises at least one hydrocolloid, and then    -   removing the moulded product from the mould form.

In a preferred embodiment of the disclosure the binder further comprisesat least one fatty acid ester of glycerol.

In an embodiment of the disclosure, the mould form comprises a firstmoulding part having a first moulding shape and a second moulding parthaving a second moulding part being closed around the mixture.

In some embodiment it may be found advantageous that the method furthercomprises the step of compressing the mixture in the mould form betweenthe first moulding part and the second moulding part.

In some embodiments, it is found advantageous that the mixture is formedinto a web, which is then provided into the mould form. The provisionmay be by closing the mould parts around the web and then if appropriateapply pressure and then a cutting action to form the moulded product.

In a further aspect of the disclosure, there is also provided a methodof producing a tubular mineral wool insulation product, said methodcomprising the steps of:

-   -   producing a web comprising a mixture of a portion of mineral        fibres and a binder composition, and    -   applying said web around a core;    -   curing the binder composition, wherein the binder composition        comprises at least one hydrocolloid, and then    -   removing the tubular mineral wool insulation product from the        core.

In a preferred embodiment of this aspect of the disclosure the bindercomposition further comprises at least one fatty acid ester of glycerol.

The web may be folded longitudinally around a core to form a tubularproduct. Alternatively, the application of the web around a core is doneby winding said web around a core mandrel.

In one embodiment, the binder composition in the mixture of the web isuncured before the web is applied around the core. The bindercomposition may then be cured before the product is removed from thecore mandrel.

In another embodiment, the binder composition in the mixture of the webis cured before winding the web around the mandrel, and a further bindercomposition comprising at least one hydrocolloid is applied to the web,e.g. by spraying, during the step of winding the web around the mandrel.Here, the further uncured binder composition is sprayed onto the web andthereby the binder composition can be used as an adhesive for bindingthe two layers, i.e. two windings, to each other. The adhesive bindercomposition can then be cured resulting in a strong bond between thelayers in the tubular product.

Subsequent to or just before the removal of the tubular product from themandrel the method may preferably also comprise the step of cutting theends of the tubular mineral wool insulation product to provide theproduct in a predetermined length. A metal foil may also be appliedaround the tubular mineral wool product.

Various embodiments of the binder composition used in the disclosure aredefined in the further dependent claims.

The disclosure also relates to various mineral wool products provided bythe method described above.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure is explained with reference to the accompanying drawings,in which:

FIGS. 1 to 3 are sequential schematic cross-sectional views of amoulding process according to one embodiment of this disclosure;

FIGS. 4 and 5 show a second embodiment of the disclosure; and

FIG. 6 shows a third embodiment of the disclosure.

DETAILED DESCRIPTION OF THE INVENTION

The Mineral Wool Element

Mineral wool elements generally comprise man-made vitreous fibres (MMVF)such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag wool,mineral wool and stone wool, which are bonded together by a curedmineral wool binder which conventionally is a thermoset polymeric bindermaterial. For use as thermal or acoustical insulation products, bondedmineral fibre mats are generally produced by converting a melt made ofsuitable raw materials to fibres in conventional manner, for instance bya spinning cup process or by a cascade rotor process. The fibres areblown into a forming chamber and, while airborne and while still hot,are sprayed with a binder solution and randomly deposited as a mat orweb onto a travelling conveyor. The fibre web is then transferred to acuring oven where heated air is blown through the web to cure the binderand rigidly bond the mineral fibres together.

If desired, the web may be subjected to the shaping process beforecuring. The bonded mineral fibre element may be cut to a desired formate.g., in the form of a batt. Thus, the mineral wool elements, forinstance, have the form of woven and nonwoven fabrics, mats, batts,slabs, sheets, plates, strips, rolls, granulates and other shapedarticles which find use for example, as thermal or acoustical insulationmaterials, vibration damping, construction materials, facade insulation,reinforcing materials for roofing or flooring applications, as filterstock, as horticultural growing media and in other applications.

For the moulded mineral wool products the mineral wool may alternativelybe provided with an uncured binder to a mould, whereafter the binder iscured while the material is in the mould.

The Mineral Wool Binder Composition

The binder composition in the present disclosure comprises at least onehydrocolloid. In a preferred embodiment the binder composition alsocomprises at least one fatty acid ester of glycerol.

In a preferred embodiment, the binders used in the present disclosureare formaldehyde free.

For the purpose of the present application, the term “formaldehyde free”is defined to characterize a mineral wool product where the emission isbelow 5 μg/m²/h of formaldehyde from the mineral wool product,preferably below 3 μg/m²/h. Preferably, the test is carried out inaccordance with ISO 16000 for testing aldehyde emissions.

A surprising advantage of embodiments of mineral wool products accordingto the present disclosure is that they show self-healing properties.After being exposed to very harsh conditions, where mineral woolproducts loose a part of their strength, the mineral wool productsaccording to the present disclosure can regain a part of, the whole ofor even exceed the original strength. In one embodiment, the agedstrength is at least 80%, such as at least 90%, such as at least 100%,such as at least 130%, such as at least 150% of the unaged strength.This is in contrast to conventional mineral wool products for which theloss of strength after being exposed to harsh environmental conditionsis irreversible. While not wanting to be bound to any particular theory,the present inventors believe that this surprising property in mineralwool products according to the present disclosure is due to the complexnature of the bonds formed in the network of the cured bindercomposition, such as the protein crosslinked by the phenol and/orquinone containing compound or crosslinked by an enzyme, which alsoincludes quaternary structures and hydrogen bonds and allows bonds inthe network to be established after returning to normal environmentalconditions. For an insulation product, which when e.g. used in a car canbe exposed to very high temperatures in the summer, this is an importantadvantage for the long term stability of the product.

Hydrocolloid

Hydrocolloids are hydrophilic polymers, of vegetable, animal, microbialor synthetic origin, that generally contain many hydroxyl groups and maybe polyelectrolytes. They are widely used to control the functionalproperties of aqueous foodstuffs.

Hydrocolloids may be proteins or polysaccharides and are fully orpartially soluble in water and are used principally to increase theviscosity of the continuous phase (aqueous phase) i.e. as gelling agentor thickener. They can also be used as emulsifiers since theirstabilizing effect on emulsions derives from an increase in viscosity ofthe aqueous phase.

A hydrocolloid usually consists of mixtures of similar, but notidentical molecules and arising from different sources and methods ofpreparation. The thermal processing and for example, salt content, pHand temperature all affect the physical properties they exhibit.Descriptions of hydrocolloids often present idealised structures butsince they are natural products (or derivatives) with structuresdetermined by for example stochastic enzymatic action, not laid downexactly by the genetic code, the structure may vary from the idealisedstructure.

Many hydrocolloids are polyelectrolytes (for example alginate, gelatin,carboxymethylcellulose and xanthan gum).

Polyelectrolytes are polymers where a significant number of therepeating units bear an electrolyte group. Polycations and polyanionsare polyelectrolytes. These groups dissociate in aqueous solutions(water), making the polymers charged. Polyelectrolyte properties arethus similar to both electrolytes (salts) and polymers (high molecularweight compounds) and are sometimes called polysalts.

The charged groups ensure strong hydration, particularly on aper-molecule basis. The presence of counterions and co-ions (ions withthe same charge as the polyelectrolyte) introduce complex behavior thatis ion-specific.

A proportion of the counterions remain tightly associated with thepolyelectrolyte, being trapped in its electrostatic field and soreducing their activity and mobility.

In one embodiment the binder composition comprise one or morecounter-ion(s) selected from the group of Mg2+, Ca2+, Sr2+, Ba2+.

Another property of a polyelectrolyte is the high linear charge density(number of charged groups per unit length).

Generally neutral hydrocolloids are less soluble whereaspolyelectrolytes are more soluble.

Many hydrocolloids also gel. Gels are liquid-water-containing networksshowing solid-like behavior with characteristic strength, dependent ontheir concentration, and hardness and brittleness dependent on thestructure of the hydrocolloid(s) present.

Hydrogels are hydrophilic crosslinked polymers that are capable ofswelling to absorb and hold vast amounts of water. They are particularlyknown from their use in sanitary products. Commonly used materials makeuse of polyacrylates, but hydrogels may be made by crosslinking solublehydrocolloids to make an insoluble but elastic and hydrophilic polymer.

Examples of hydrocolloids comprise: Agar agar, Alginate, Arabinoxylan,Carrageenan, Carboxymethylcellulose, Cellulose, Curdlan, Gelatin,Gellan, β-Glucan, Guar gum, Gum arabic, Locust bean gum, Pectin, Starch,Xanthan gum. In one embodiment, the at least one hydrocolloid isselected from the group consisting of gelatin, pectin, starch, alginate,agar agar, carrageenan, gellan gum, guar gum, gum arabic, locust beangum, xanthan gum, cellulose derivatives such as carboxymethylcellulose,arabinoxylan, cellulose, curdlan, β-glucan.

Examples of polyelectrolytic hydrocolloids comprise: gelatin, pectin,alginate, carrageenan, gum arabic, xanthan gum, cellulose derivativessuch as carboxymethylcellulose.

In one embodiment, the at least one hydrocolloid is a polyelectrolytichydrocolloid.

In one embodiment, the at least one hydrocolloid is selected from thegroup consisting of gelatin, pectin, alginate, carrageenan, gum arabic,xanthan gum, cellulose derivatives such as carboxymethylcellulose.

In one embodiment, the at least one hydrocolloid is a gel former.

In one embodiment, the at least one hydrocolloid is used in form of asalt, such as a salt of Na+, K+, NH4+, Mg2+, Ca2+, Sr2+, Ba2+.

Gelatin

Gelatin is derived from chemical degradation of collagen. Gelatin mayalso be produced by recombinant techniques. Gelatin is water soluble andhas a molecular weight of 10.000 to 500.000 g/mol, such as 30.000 to300.000 g/mol dependent on the grade of hydrolysis. Gelatin is a widelyused food product and it is therefore generally accepted that thiscompound is totally non-toxic and therefore no precautions are to betaken when handling gelatin.

Gelatin is a heterogeneous mixture of single or multi-strandedpolypeptides, typically showing helix structures. Specifically, thetriple helix of type I collagen extracted from skin and bones, as asource for gelatin, is composed of two α1(I) and one α2(I) chains.

Gelatin solutions may undergo coil-helix transitions.

A type gelatins are produced by acidic treatment. B type gelatins areproduced by basic treatment.

Chemical cross-links may be introduced to gelatin. In one embodiment,transglutaminase is used to link lysine to glutamine residues; in oneembodiment, glutaraldehyde is used to link lysine to lysine, in oneembodiment, tannins are used to link lysine residues.

The gelatin can also be further hydrolysed to smaller fragments of downto 3000 g/mol.

On cooling a gelatin solution, collagen like helices may be formed.

Other hydrocolloids may also comprise helix structures such as collagenlike helices. Gelatin may form helix structures.

In one embodiment, the cured binder comprising hydrocolloid compriseshelix structures.

In one embodiment, the at least one hydrocolloid is a low strengthgelatin, such as a gelatin having a gel strength of 30 to 125 Bloom.

In one embodiment, the at least one hydrocolloid is a medium strengthgelatin, such as a gelatin having a gel strength of 125 to 180 Bloom.

In one embodiment, the at least one hydrocolloid is a high strengthgelatin, such as a gelatin having a gel strength of 180 to 300 Bloom.

In a preferred embodiment, the gelatin is preferably originating fromone or more sources from the group consisting of mammal, bird species,such as from cow, pig, horse, fowl, and/or from scales, skin of fish.

In one embodiment, urea may be added to the binder compositions used inthe present disclosure. The inventors have found that the addition ofeven small amounts of urea causes denaturation of the gelatin, which canslow down the gelling, which might be desired in some embodiments. Theaddition of urea might also lead to a softening of the product.

The inventors have found that the carboxylic acid groups in gelatinsinteract strongly with trivalent and tetravalent ions, for examplealuminum salts. This is especially true for type B gelatins whichcontain more carboxylic acid groups than type A gelatins.

The present inventors have found that in some embodiments, curing/dryingof binder compositions used in the present disclosure including gelatinshould not start off at very high temperatures.

The inventors have found that starting the curing at low temperaturesmay lead to stronger products. Without being bound to any particulartheory, it is assumed by the inventors that starting curing at hightemperatures may lead to an impenetrable outer shell of the bindercomposition which hinders water from underneath to get out.

Surprisingly, the binders used in the present disclosure includinggelatins are very heat resistant. The present inventors have found thatin some embodiments the cured binders can sustain temperatures up to300° C. without degradation.

Pectin

Pectin is a heterogeneous grouping of acidic structural polysaccharides,found in fruit and vegetables which form acid-stable gels.

Generally, pectins do not possess exact structures, instead it maycontain up to 17 different monosaccharides and over 20 types ofdifferent linkages.

D-galacturonic acid residues form most of the molecules.

Gel strength increases with increasing Ca2+ concentration but reduceswith temperature and acidity increase (pH<3).

Pectin may form helix structures.

The gelling ability of the di-cations is similar to that found withalginates (Mg2+ is much less than for Ca2+, Sr2+ being less than forBa2+).

Alginate

Alginates are scaffolding polysaccharides produced by brown seaweeds.

Alginates are linear unbranched polymers containing β-(1,4)-linkedD-mannuronic acid (M) and α-(1,4)-linked L-guluronic acid (G) residues.Alginate may also be a bacterial alginate, such as which areadditionally O-acetylated. Alginates are not random copolymers but,according to the source algae, consist of blocks of similar and strictlyalternating residues (that is, MMMMMM, GGGGGG and GMGMGMGM), each ofwhich have different conformational preferences and behavior. Alginatesmay be prepared with a wide range of average molecular weights(50-100000 residues). The free carboxylic acids have a water moleculeH3O+ firmly hydrogen bound to carboxylate. Ca2+ ions can replace thishydrogen bonding, zipping guluronate, but not mannuronate, chainstogether stoichiometrically in a so-called egg-box like conformation.Recombinant epimerases with different specificities may be used toproduce designer alginates.

Alginate may form helix structures.

Carrageenan

Carrageenan is a collective term for scaffolding polysaccharidesprepared by alkaline extraction (and modification) from red seaweed.

Carrageenans are linear polymers of about 25,000 galactose derivativeswith regular but imprecise structures, dependent on the source andextraction conditions.

κ-carrageenan (kappa-carrageenan) is produced by alkaline eliminationfrom μ-carrageenan isolated mostly from the tropical seaweed Kappaphycusalvarezii (also known as Eucheuma cottonii).

ι-carrageenan (iota-carrageenan) is produced by alkaline eliminationfrom ν-carrageenan isolated mostly from the Philippines seaweed Eucheumadenticulatum (also called Spinosum).

λ-carrageenan (lambda-carrageenan) (isolated mainly from Gigartinapistillata or Chondrus crispus) is converted into θ-carrageenan(theta-carrageenan) by alkaline elimination, but at a much slower ratethan causes the production of ι-carrageenan and κ-carrageenan.

The strongest gels of κ-carrageenan are formed with K+ rather than Li+,Na+, Mg2+, Ca2+, or Sr2+.

All carrageenans may form helix structures.

Gum Arabic

Gum arabic is a complex and variable mixture of arabinogalactanoligosaccharides, polysaccharides and glycoproteins. Gum arabic consistsof a mixture of lower relative molecular mass polysaccharide and highermolecular weight hydroxyproline-rich glycoprotein with a widevariability.

Gum arabic has a simultaneous presence of hydrophilic carbohydrate andhydrophobic protein.

Xanthan Gum

Xanthan gum is a microbial desiccation-resistant polymer prepared e.g.by aerobic submerged fermentation from Xanthomonas campestris.

Xanthan gum is an anionic polyelectrolyte with a β-(1,4)-D-glucopyranoseglucan (as cellulose) backbone with side chains of -(3,1)-α-linkedD-mannopyranose-(2,1)-β-D-glucuronic acid-(4,1)-β-D-mannopyranose onalternating residues.

Xanthan gums natural state has been proposed to be bimolecularantiparallel double helices. A conversion between the ordered doublehelical conformation and the single more-flexible extended chain maytake place at between 40° C.-80° C. Xanthan gums may form helixstructures.

Xanthan gums may contain cellulose.

Cellulose Derivatives

An example of a cellulose derivative is carboxymethylcellulose.

Carboxymethylcellulose (CMC) is a chemically modified derivative ofcellulose formed by its reaction with alkali and chloroacetic acid.

The CMC structure is based on the β-(1,4)-D-glucopyranose polymer ofcellulose. Different preparations may have different degrees ofsubstitution, but it is generally in the range 0.6-0.95 derivatives permonomer unit.

Agar Agar

Agar agar is a scaffolding polysaccharide prepared from the same familyof red seaweeds (Rhodophycae) as the carrageenans. It is commerciallyobtained from species of Gelidium and Gracilariae.

Agar agar consists of a mixture of agarose and agaropectin. Agarose is alinear polymer, of relative molecular mass (molecular weight) about120,000, based on the-(1,3)-β-D-galactopyranose-(1,4)-3,6-anhydro-α-L-galactopyranose unit.

Agaropectin is a heterogeneous mixture of smaller molecules that occurin lesser amounts.

Agar agar may form helix structures.

Arabinoxylan

Arabinoxylans are naturally found in the bran of grasses (Graminiae).

Arabinoxylans consist of α-L-arabinofuranose residues attached asbranch-points to β-(1,4)-linked D-xylopyranose polymeric backbonechains.

Arabinoxylan may form helix structures.

Cellulose

Cellulose is a scaffolding polysaccharide found in plants asmicrofibrils (2-20 nm diameter and 100-40 000 nm long). Cellulose ismostly prepared from wood pulp. Cellulose is also produced in a highlyhydrated form by some bacteria (for example, Acetobacter xylinum).

Cellulose is a linear polymer of β-(1,4)-D-glucopyranose units in 4Clconformation. There are four crystalline forms, Iα, Iβ, II and III.

Cellulose derivatives may be methyl cellulose, hydroxypropylmethylcellulose, hydroxyethyl methylcellulose, hydroxyethyl cellulose,hydroxypropyl cellulose.

Curdlan

Curdlan is a polymer prepared commercially from a mutant strain ofAlcaligenes faecalis var. myxogenes. Curdlan (curdlan gum) is a moderaterelative molecular mass, unbranched linear 1,3 β-D glucan with noside-chains.

Curdlan may form helix structures.

Curdlan gum is insoluble in cold water but aqueous suspensionsplasticize and briefly dissolve before producing reversible gels onheating to around 55° C. Heating at higher temperatures produces moreresilient irreversible gels, which then remain on cooling.

Scleroglucan is also a 1,3 β-D glucan but has additional 1,6 β-linksthat confer solubility under ambient conditions.

Gellan

Gellan gum is a linear tetrasaccharide4)-L-rhamnopyranosyl-(α-1,3)-D-glucopyranosyl-(β-1,4)-D-glucuronopyranosyl-(β-1,4)-D-glucopyranosyl-(β-1,with O(2) L-glyceryl and O(6) acetyl substituents on the 3-linkedglucose.

Gellan may form helix structures.

β-Glucan

β-Glucans occur in the bran of grasses (Gramineae).

β-Glucans consist of linear unbranched polysaccharides of linkedβ-(1,3)- and β-(1,4)-D-glucopyranose units in a non-repeating butnon-random order.

Guar Gum

Guar gum (also called guaran) is a reserve polysaccharide (seed flour)extracted from the seed of the leguminous shrub Cyamopsis tetragonoloba.

Guar gum is a galactomannana similar to locust bean gum consisting of a(1,4)-linked β-D-mannopyranose backbone with branch points from their6-positions linked to α-D-galactose (that is,1,6-linked-α-D-galactopyranose).

Guar gum is made up of non-ionic polydisperse rod-shaped polymer.

Unlike locust bean gum, it does not form gels.

Locust Bean Gum

Locust bean gum (also called Carob bean gum and Carubin) is a reservepolysaccharide (seed flour) extracted from the seed (kernels) of thecarob tree (Ceratonia siliqua).

Locust bean gum is a galactomannana similar to guar gum consisting of a(1,4)-linked β-D-mannopyranose backbone with branch points from their6-positions linked to α-D-galactose (that is, 1,6-linkedα-D-galactopyranose).

Locust bean gum is polydisperse consisting of non-ionic molecules.

Starch

Starch consists of two types of molecules, amylose (normally 20-30%) andamylopectin (normally 70-80%). Both consist of polymers of α-D-glucoseunits in the 4Cl conformation. In amylose these are linked -(1,4)-, withthe ring oxygen atoms all on the same side, whereas in amylopectin aboutone residue in every twenty or so is also linked -(1,6)- formingbranch-points. The relative proportions of amylose to amylopectin and-(1,6)- branch-points both depend on the source of the starch. Thestarch may derive from the source of corn (maize), wheat, potato,tapioca and rice. Amylopectin (without amylose) can be isolated from‘waxy’ maize starch whereas amylose (without amylopectin) is bestisolated after specifically hydrolyzing the amylopectin withpullulanase.

Amylose may form helix structures.

In one embodiment, the at least one hydrocolloid is a functionalderivative of starch such as cross-linked, oxidized, acetylated,hydroxypropylated and partially hydrolyzed starch.

In a preferred embodiment, the binder composition comprises at least twohydrocolloids, wherein one hydrocolloid is gelatin and the at least oneother hydrocolloid is selected from the group consisting of pectin,starch, alginate, agar agar, carrageenan, gellan gum, guar gum, gumarabic, locust bean gum, xanthan gum, cellulose derivatives such ascarboxymethylcellulose, arabinoxylan, cellulose, curdlan, β-glucan.

In one embodiment, the binder composition comprises at least twohydrocolloids, wherein one hydrocolloid is gelatin and the at leastother hydrocolloid is pectin.

In one embodiment, the binder composition comprises at least twohydrocolloids, wherein one hydrocolloid is gelatin and the at leastother hydrocolloid is alginate.

In one embodiment, the binder composition comprises at least twohydrocolloids, wherein one hydrocolloid is gelatin and the at leastother hydrocolloid is carboxymethylcellulose.

In a preferred embodiment, the binder composition used in the presentdisclosure comprises at least two hydrocolloids, wherein onehydrocolloid is gelatin and wherein the gelatin is present in theaqueous binder composition in an amount of 10 to 95 wt.-%, such as 20 to80 wt.-%, such as 30 to 70 wt.-%, such as 40 to 60 wt.-%, based on theweight of the hydrocolloids.

In one embodiment, the binder composition comprises at least twohydrocolloids, wherein the one hydrocolloid and the at least otherhydrocolloid have complementary charges.

In one embodiment, the one hydrocolloid is one or more of gelatin or gumarabic having complementary charges from one or more hydrocolloid(s)selected from the group of pectin, alginate, carrageenan, xanthan gum orcarboxymethylcellulose.

In one embodiment, the binder composition is capable of curing at atemperature of not more than 95° C., such as 5-95° C., such as 10-80°C., such as 20-60° C., such as 40-50° C.

In one embodiment, the aqueous binder composition used in the presentdisclosure is not a thermoset binder.

A thermosetting composition is in a soft solid or viscous liquid state,preferably comprising a prepolymer, preferably comprising a resin, thatchanges irreversibly into an infusible, insoluble polymer network bycuring. Curing is typically induced by the action of heat, wherebytypically temperatures above 95° C. are needed.

A cured thermosetting resin is called a thermoset or a thermosettingplastic/polymer—when used as the bulk material in a polymer composite,they are referred to as the thermoset polymer matrix. In one embodiment,the aqueous binder composition used in the present disclosure does notcontain a poly(meth)acrylic acid, a salt of a poly(meth)acrylic acid oran ester of a poly(meth)acrylic acid.

In one embodiment, the at least one hydrocolloid is a biopolymer ormodified biopolymer.

Biopolymers are polymers produced by living organisms. Biopolymers maycontain monomeric units that are covalently bonded to form largerstructures.

There are three main classes of biopolymers, classified according to themonomeric units used and the structure of the biopolymer formed:Polynucleotides (RNA and DNA), which are long polymers composed of 13 ormore nucleotide monomers; Polypeptides, such as proteins, which arepolymers of amino acids; Polysaccharides, such as linearly bondedpolymeric carbohydrate structures.

Polysaccharides may be linear or branched; they are typically joinedwith glycosidic bonds. In addition, many saccharide units can undergovarious chemical modifications, and may form parts of other molecules,such as glycoproteins.

In one embodiment, the at least one hydrocolloid is a biopolymer ormodified biopolymer with a polydispersity index regarding molecular massdistribution of 1, such as 0.9 to 1.

In one embodiment, the binder composition comprises proteins from animalsources, including collagen, gelatin, and hydrolysed gelatin, and thebinder composition further comprises at least one phenol and/or quinonecontaining compound, such as tannin selected from one or more componentsfrom the group consisting of tannic acid, condensed tannins(proanthocyanidins), hydrolysable tannins, gallotannins, 7ellagitannins, complex tannins, and/or tannin originating from one ormore of oak, chestnut, staghorn sumac and fringe cups.

In one embodiment, the binder composition comprises proteins from animalsources, including collagen, gelatin, and hydrolysed gelatin, andwherein the binder composition further comprises at least one enzymeselected from the group consisting of transglutaminase (EC 2.3.2.13),protein disulfide isomerase (EC 5.3.4.1), thiol oxidase (EC 1.8.3.2),polyphenol oxidase (EC 1.14.18.1), in particular catechol oxidase,tyrosine oxidase, and phenoloxidase, lysyl oxidase (EC 1.4.3.13), andperoxidase (EC 1.11.1.7).

Fatty Acid Ester of Glycerol

In a preferred embodiment the binder composition also comprises acomponent in form of at least one fatty acid ester of glycerol.

A fatty acid is a carboxylic acid with an aliphatic chain, which iseither saturated or unsaturated.

Glycerol is a polyol compound having the IUPAC name propane-1,2,3-triol.

Naturally occurring fats and oils are glycerol esters with fatty acids(also called triglycerides).

For the purpose of the present disclosure, the term fatty acid ester ofglycerol refers to mono-, di-, and tri-esters of glycerol with fattyacids.

While the term fatty acid can in the context of the present disclosurebe any carboxylic acid with an aliphatic chain, it is preferred that itis carboxylic acid with an aliphatic chain having 4 to 28 carbon atoms,preferably of an even number of carbon atoms. Preferably, the aliphaticchain of the fatty acid is unbranched.

In a preferred embodiment, the at least one fatty acid ester of glycerolis in form of a plant oil and/or animal oil. In the context of thepresent disclosure, the term “oil” comprises at least one fatty acidester of glycerol in form of oils or fats.

In one preferred embodiment, the at least one fatty acid ester ofglycerol is a plant-based oil.

In a preferred embodiment, the at least one fatty acid ester of glycerolis in form of fruit pulp fats such as palm oil, olive oil, avocado oil;seed-kernel fats such as lauric acid oils, such as coconut oil, palmkernel oil, babassu oil and other palm seed oils, other sources oflauric acid oils; palmitic-stearic acid oils such as cocoa butter, sheabutter, borneo tallow and related fats (vegetable butters); palmiticacid oils such as cottonseed oil, kapok and related oils, pumpkin seedoil, corn (maize) oil, cereal oils; oleic-linoleic acid oils such assunflower oil, sesame oil, linseed oil, perilla oil, hempseed oil,teaseed oil, safflower and niger seed oils, grape-seed oil, poppyseedoil, leguminous oil such as soybean oil, peanut oil, lupine oil;cruciferous oils such as rapeseed oil, mustard seed oil; conjugated acidoils such as tung oil and related oils, oiticica oil and related oils;substituted fatty acid oils such as castor oil, chaulmoogra, hydnocarpusand gorli oils, vernonia oil; animal fats such as land-animal fats suchas lard, beef tallow, mutton tallow, horse fat, goose fat, chicken fat;marine oils such as whale oil and fish oil.

In a preferred embodiment, the at least one fatty acid ester of glycerolis in form of a plant oil, in particular selected from one or morecomponents from the group consisting of linseed oil, olive oil, tungoil, coconut oil, hemp oil, rapeseed oil, and sunflower oil.

In a preferred embodiment, the at least one fatty acid ester of glycerolis selected from one or more components from the group consisting of aplant oil having an iodine number in the range of approximately 136 to178, such as a linseed oil having an iodine number in the range ofapproximately 136 to 178, a plant oil having an iodine number in therange of approximately 80 to 88, such as an olive oil having an iodinenumber in the range of approximately 80 to 88, a plant oil having aniodine number in the range of approximately 163 to 173, such as tung oilhaving an iodine number in the range of approximately 163 to 173, aplant oil having an iodine number in the range of approximately 7 to 10,such as coconut oil having an iodine number in the range ofapproximately 7 to 10, a plant oil having an iodine number in the rangeof approximately 140 to 170, such as hemp oil having an iodine number inthe range of approximately 140 to 170, a plant oil having an iodinenumber in the range of approximately 94 to 120, such as a rapeseed oilhaving an iodine number in the range of approximately 94 to 120, a plantoil having an iodine number in the range of approximately 118 to 144,such as a sunflower oil having an iodine number in the range ofapproximately 118 to 144.

In one embodiment, the at least one fatty acid ester of glycerol is notof natural origin.

In one embodiment, the at least one fatty acid ester of glycerol is amodified plant or animal oil.

In one embodiment, the at least one fatty acid ester of glycerolcomprises at least one trans-fatty acid.

In an alternative preferred embodiment, the at least one fatty acidester of glycerol is in form of an animal oil, such as a fish oil.

The present inventors have found that an important parameter for thefatty acid ester of glycerol used in the binders in the presentdisclosure is the amount of unsaturation in the fatty acid. The amountof unsaturation in fatty acids is usually measured by the iodine number(also called iodine value or iodine absorption value or iodine index).The higher the iodine number, the more C═C bonds are present in thefatty acid. For the determination of the iodine number as a measure ofthe unsaturation of fatty acids, we make reference to Thomas, Alfred(2002) “Fats and fatty oils” in Ullmann's Encyclopedia of industrialchemistry, Weinheim, Wiley-VCH.

In a preferred embodiment, the at least one fatty acid ester of glycerolcomprises a plant oil and/or animal oil having a iodine number of ≥75,such as 75 to 180, such as ≥130, such as 130 to 180.

In an alternative preferred embodiment, the at least one fatty acidester of glycerol comprises a plant oil and/or animal oil having aiodine number of ≤100, such as ≤25.

In one embodiment, the at least one fatty acid ester of glycerol is adrying oil. For a definition of a drying oil, see Poth, Ulrich (2012)“Drying oils and related products” in Ullmann's Encyclopedia ofindustrial chemistry, Weinheim, Wiley-VCH.

Accordingly, the present inventors have found that particularly goodresults are achieved when the iodine number is either in a fairly highrange or, alternatively, in a fairly low range. While not wanting to bebound by any particular theory, the present inventors assume that theadvantageous properties inflicted by the fatty acid esters of highiodine number on the one hand and low iodine number on the other handare based on different mechanisms. The present inventors assume that theadvantageous properties of glycerol esters of fatty acids having a highiodine number might be due to the participation of the C═C double-bondsfound in high numbers in these fatty acids in a crosslinking reaction,while the glycerol esters of fatty acids having a low iodine number andlacking high amounts of C═C double-bonds might allow a stabilization ofthe cured binder by van der Waals interactions.

In a preferred embodiment, the content of the fatty acid ester ofglycerol is 0.5 to 40, such as 1 to 30, such as 1.5 to 20, such as 3 to10, such as 4 to 7.5 wt.-%, based on dry hydrocolloid basis.

In one embodiment, the binder composition comprises gelatin, and thebinder composition further comprises a tannin selected from one or morecomponents from the group consisting of tannic acid, condensed tannins(proanthocyanidins), hydrolysable tannins, gallotannins, ellagitannins,complex tannins, and/or tannin originating from one or more of oak,chestnut, staghorn sumac and fringe cups, preferably tannic acid, andthe binder composition further comprises at least one fatty acid esterof glycerol, such as at least one fatty acid ester of glycerol selectedfrom one or more components from the group consisting of linseed oil,olive oil, tung oil, coconut oil, hemp oil, rapeseed oil, and sunfloweroil.

In one embodiment, the binder composition comprises gelatin, and thebinder composition further comprises at least one enzyme which is atransglutaminase (EC 2.3.2.13), and the binder composition furthercomprises at least one fatty acid ester of glycerol, such as at leastone fatty acid ester of glycerol selected from one or more componentsfrom the group consisting of linseed oil, olive oil, tung oil, coconutoil, hemp oil, rapeseed oil, and sunflower oil.

In one embodiment, the aqueous binder composition is formaldehyde-free.

In one embodiment, the binder composition is consisting essentially of:

-   -   at least one hydrocolloid;    -   at least one fatty acid ester of glycerol;    -   optionally at least one pH-adjuster;    -   optionally at least one crosslinker;    -   optionally at least one anti-fouling agent;    -   optionally at least one anti-swelling agent;    -   water.

In one embodiment, an oil may be added to the binder composition.

In one embodiment, the at least one oil is a non-emulsified hydrocarbonoil.

In one embodiment, the at least one oil is an emulsified hydrocarbonoil.

In one embodiment, the at least one oil is a plant-based oil.

In one embodiment, the at least one crosslinker is tannin selected fromone or more components from the group consisting of tannic acid,condensed tannins (proanthocyanidins), hydrolysable tannins,gallotannins, ellagitannins, complex tannins, and/or tannin originatingfrom one or more of oak, chestnut, staghorn sumac and fringe cups.

In one embodiment, the at least one crosslinker is an enzyme selectedfrom the group consisting of transglutaminase (EC 2.3.2.13), proteindisulfide isomerase (EC 5.3.4.1), thiol oxidase (EC 1.8.3.2), polyphenoloxidase (EC 1.14.18.1), in particular catechol oxidase, tyrosineoxidase, and phenoloxidase, lysyl oxidase (EC 1.4.3.13), and peroxidase(EC 1.11.1.7).

In one embodiment, the at least one anti-swelling agent is tannic acidand/or tannins.

In one embodiment, the at least one anti-fouling agent is anantimicrobial agent.

Antimicrobial agents may be benzoic acid, propionic acid, sodiumbenzoate, sorbic acid, and potassium sorbate to inhibit the outgrowth ofboth bacterial and fungal cells. However, natural biopreservatives maybe used. Chitosan is regarded as being antifungal and antibacterial. Themost frequently used biopreservatives for antimicrobial are lysozyme andnisin. Common other biopreservatives that may be used are bacteriocins,such as lacticin and pediocin and antimicrobial enzymes, such aschitinase and glucose oxidase. Also, the use of the enzymelactoperoxidase (LPS) presents antifungal and antiviral activities.Natural antimicrobial agents may also be used, such as tannins,rosemary, and garlic essential oils, oregano, lemon grass, or cinnamonoil at different concentrations.

Mineral Fibre Product

In the moulded mineral wool product according to the disclosure themineral fibres are bound by a binder resulting from the curing of abinder composition as described above.

In one embodiment, the loss on ignition (LOI) of the mineral woolproduct according to the present disclosure is within the range of 0.1to 25.0%, such as 0.3 to 18.0%, such as 0.5 to 12.0%, such as 0.7 to8.0% by weight.

In one embodiment, the binder is not crosslinked.

In an alternative embodiment, the binder is crosslinked.

Reaction of the Binder Components

The present inventors have found that in some embodiments of the mineralwool product according to the present disclosure are best to be producedwhen the binder is applied to the mineral fibres under acidicconditions. Therefore, in a preferred embodiment, the binder applied tothe mineral fibres comprises a pH-adjuster, in particular in form of apH buffer.

In a preferred embodiment, the binder in its uncured state has a pHvalue of less than 8, such as less than 7, such as less than 6.

The present inventors have found that in some embodiments, the curing ofthe binder is strongly accelerated under alkaline conditions. Therefore,in one embodiment, the binder composition for mineral fibres comprises apH-adjuster, preferably in form of a base, such as organic base, such asamine or salts thereof, inorganic bases, such as metal hydroxide, suchas KOH or NaOH, ammonia or salts thereof.

In a particular preferred embodiment, the pH adjuster is an alkalinemetal hydroxide, in particular NaOH.

In a preferred embodiment, the binder composition used in to the presentdisclosure has a pH of 7 to 10, such as 7.5 to 9.5, such as 8 to 9.

Other additives may be components such as one or more reactive ornonreactive silicones and may be added to the binder. Preferably, theone or more reactive or nonreactive silicone is selected from the groupconsisting of silicone constituted of a main chain composed oforganosiloxane residues, especially diphenylsiloxane residues,alkylsiloxane residues, preferably dimethylsiloxane residues, bearing atleast one hydroxyl, acyl, carboxyl or anhydride, amine, epoxy or vinylfunctional group capable of reacting with at least one of theconstituents of the binder composition and is preferably present in anamount of 0.1-15 weight-%, preferably from 0.1-10 weight-%, morepreferably 0.3-8 weight-%, based on the total binder mass.

In one embodiment, an anti-fouling agent may be added to the binder.

In a preferred embodiment, the anti-fouling agent is a tannin, inparticular a tannin selected from one or more components from the groupconsisting of tannic acid, condensed tannins (proanthocyanidins),hydrolysable tannins, gallotannins, ellagitannins, complex tannins,and/or tannin originating from one or more of oak, chestnut, staghornsumac and fringe cups.

In one embodiment, an anti-swelling agent may be added to the binder,such as tannic acid and/or tannins.

Further additives may be additives containing calcium ions andantioxidants.

In one embodiment, the binder composition used in the present disclosurecontains additives in form of linkers containing acyl groups and/oramine groups and/or thiol groups. These linkers can strengthen and/ormodify the network of the cured binder.

In one embodiment, the binder compositions used in the presentdisclosure contain further additives in form of additives selected fromthe group consisting of PEG-type reagents, silanes, andhydroxylapatites.

Properties of the Mineral Wool Product

In a preferred embodiment, the density of the moulded mineral woolproduct is in the range of 10-1200 kg/m³, such as 30-800 kg/m³, such as40-600 kg/m³, such as 50-250 kg/m³, such as 60-200 kg/m³.

Method of Producing a Moulded Mineral Wool Product

The present disclosure provides a method for producing a moulded mineralwool product by binding mineral fibres with the binder composition.

Accordingly, the present disclosure is directed to a method forproducing a moulded mineral wool product which comprises the steps ofcontacting mineral fibres with a binder composition comprising at leastone hydrocolloid, and preferably also at least one fatty acid ester ofglycerol and curing the binder.

In one embodiment, the curing process comprises a drying process, inparticular by blowing air or gas over/through the mineral wool productor by increasing temperature.

The present disclosure is also directed to a mineral wool productprepared by a method as described above.

Preferably, the mineral wool product prepared by such a use has a losson ignition (LOI) within the range of 0.1 to 25.0%, such as 0.3 to18.0%, such as 0.5 to 12.0%, such as 0.7 to 8.0% by weight.

A particular advantage of the moulded mineral wool product according tothe present disclosure is that it does not require high temperatures forcuring. This does not only save energy, reduces VOC and obviates theneed for machinery to be highly temperature resistant, but also allowsfor a high flexibility in a process for the production of mineral woolproducts with these binders.

In one embodiment the method comprises the steps of:

-   -   making a melt of raw materials,    -   fibrerising the melt by means of a fiber forming apparatus to        form mineral fibres,    -   providing the mineral fibres in the form of a collected web,    -   mixing the binder with the mineral fibres before, during or        after the provision of the collected web to form a mixture of        mineral fibres and binder,    -   providing the mixture in a mould form,    -   curing the mixture of mineral fibres and binder.

In one embodiment, the binder is supplied in the close vicinity of thefibre forming apparatus, such as a cup spinning apparatus or a cascadespinning apparatus, in either case immediately after the fibreformation. The fibres with applied binder are thereafter conveyed onto aconveyor belt as a web.

The web may be subjected to longitudinal or length compression after thefibre formation and before substantial curing has taken place.

Fiber Forming Apparatus

There are various types of centrifugal spinners for fiberising mineralmelts.

A conventional centrifugal spinner is a cascade spinner which comprisesa sequence of a top (or first) rotor and a subsequent (or second) rotorand optionally other subsequent rotors (such as third and fourthrotors). Each rotor rotates about a different substantially horizontalaxis with a rotational direction opposite to the rotational direction ofthe or each adjacent rotor in the sequence. The different horizontalaxes are arranged such that melt which is poured on to the top rotor isthrown in sequence on to the peripheral surface of the or eachsubsequent rotor, and fibres are thrown off the or each subsequentrotor, and optionally also off the top rotor.

In one embodiment, a cascade spinner or other spinner is arranged tofiberise the melt and the fibres are entrained in air as a cloud of thefibres.

Many fiber forming apparatuses comprise a disc or cup that spins arounda substantially vertical axis. It is then conventional to arrangeseveral of these spinners in-line, i.e. substantially in the firstdirection, for instance as described in GB-A-926,749, U.S. Pat. No.3,824,086 and WO-A-83/03092.

There is usually a stream of air associated with the one or eachfiberising rotor whereby the fibres are entrained in this air as theyare formed off the surface of the rotor.

In one embodiment, binder and/or additives is added to the cloud offibres by known means. The amount of binder and/or additive may be thesame for each spinner or it may be different.

In one embodiment, a hydrocarbon oil may be added into the cloud offibres.

As used herein, the term “collected web” is intended to include anymineral fibres that have been collected together on a surface, i.e. theyare no longer entrained in air, e.g. the fibrerised mineral fibres,granulate, tufts or recycled web waste. The collected web could be aprimary web that has been formed by collection of fibres on a conveyorbelt and provided as a starting material without having beencross-lapped or otherwise consolidated.

Alternatively, the collected web could be a secondary web that has beenformed by crosslapping or otherwise consolidating a primary web.Preferably, the collected web is a primary web.

In one embodiment the mixing of the binder with the mineral fibres isdone after the provision of the collected web in the following steps:

-   -   subjecting the collected web of mineral fibres to a        disentanglement process,    -   suspending the mineral fibres in a primary air flow,    -   mixing binder composition with the mineral fibres before, during        or after the disentanglement process to form a mixture of        mineral fibres and binder.

A method of producing a mineral wool product comprising the process stepof disentanglement is described in EP10190521.

In one embodiment, the disentanglement process comprises feeding thecollected web of mineral fibres from a duct with a lower relative airflow to a duct with a higher relative air flow. In this embodiment, thedisentanglement is believed to occur, because the fibres that enter theduct with the higher relative air flow first are dragged away from thesubsequent fibres in the web. This type of disentanglement isparticularly effective for producing open tufts of fibres, rather thanthe compacted lumps that can result in an uneven distribution ofmaterials in the product.

According to a particularly preferred embodiment, the disentanglementprocess comprises feeding the collected web to at least one roller whichrotates about its longitudinal axis and has spikes protruding from itscircumferential surface. In this embodiment, the rotating roller willusually also contribute at least in part to the higher relative airflow. Often, rotation of the roller is the sole source of the higherrelative air flow.

In preferred embodiments, the mineral fibres and optionally the binderare fed to the roller from above. It is also preferred for thedisentangled mineral fibres and optionally the binder to be thrown awayfrom the roller laterally from the lower part of its circumference. Inthe most preferred embodiment, the mineral fibres are carriedapproximately 180 degrees by the roller before being thrown off.

The binder may be mixed with the mineral fibres before, during or afterthe disentanglement process. In some embodiments, it is preferred to mixthe binder with the fibres prior to the disentanglement process. Inparticular, the fibres can be in the form of an uncured collected webcontaining binder.

It is also feasible that the binder be pre-mixed with a collected web ofmineral fibres before the disentanglement process. Further mixing couldoccur during and after the disentanglement process. Alternatively, itcould be supplied to the primary air flow separately and mixed in theprimary air flow.

The mixture of mineral fibres and binder is collected from the primaryair flow by any suitable means. In one embodiment, the primary air flowis directed into the top of a cyclone chamber, which is open at itslower end and the mixture is collected from the lower end of the cyclonechamber.

The mixture of mineral fibres and binder is preferably thrown from thedisentanglement process into a forming chamber.

Having undergone the disentanglement process, the mixture of mineralfibres and binder is collected, pressed, applied to a mould and cured.Preferably, the mixture is collected on a foraminous conveyor belthaving suction means positioned below it.

In a preferred method according to the disclosure, the mixture of binderand mineral fibres, having been collected, is pressed, applied to amould and cured.

In a preferred method according to the disclosure, the mixture of binderand mineral fibres, having been collected, is scalped before beingpressed, applied to a mould and cured.

The method may be performed as a batch process, however according to anembodiment the method is performed at a mineral wool production linefeeding a primary or secondary mineral wool web into the fibreseparating process, which provides a particularly cost efficient andversatile method to provide composites having favourable mechanicalproperties and thermal insulation properties in a wide range ofdensities.

At the same time, because of the curing at ambient temperature, thelikelihood of uncured binder spots is strongly decreased.

Curing

The web is cured by a chemical and/or physical reaction of the bindercomponents. In one embodiment, the curing takes place in a curingdevice.

In one embodiment the curing is carried out at temperatures from 5 to95° C., such as 5 to 80° C., such as 5 to 60° C., such as 8 to 50° C.,such as 10 to 40° C.

In one embodiment the curing takes place in a conventional curing ovenfor mineral wool production operating at a temperature of from 5 to 95°C., such as 5 to 80° C., such as 10 to 60° C., such as 20 to 40° C.

The curing process may commence immediately after application of thebinder to the fibres. The curing is defined as a process whereby thebinder composition undergoes a physical and/or chemical reaction whichin case of a chemical reaction usually increases the molecular weight ofthe compounds in the binder composition and thereby increases theviscosity of the binder composition, usually until the bindercomposition reaches a solid state.

In one embodiment the curing process comprises cross-linking and/orwater inclusion as crystal water.

In one embodiment the cured binder contains crystal water that maydecrease in content and raise in content depending on the prevailingconditions of temperature, pressure and humidity.

In one embodiment the curing process comprises a drying process.

In a preferred embodiment, the curing of the binder composition incontact with the mineral fibers takes place in a mould.

The curing of a binder composition in contact with the mineral fibers ina mould has the particular advantage that it enables the production ofhigh-density products.

In one embodiment the curing process comprises drying by pressure. Thepressure may be applied by blowing air or gas through/over the mixtureof mineral fibres and binder. The blowing process may be accompanied byheating or cooling or it may be at ambient temperature.

In an alternative embodiment the curing process comprises application ofa vacuum to the mould. Reducing the pressure within the mould causes thebinder to dry and thereby achieve it final cured stage.

In one embodiment the curing process takes place in a humid environment.The humid environment may have a relative humidity RH of 60-99%, such as70-95%, such as 80-92%. The curing in a humid environment may befollowed by curing or drying to obtain a state of the prevalenthumidity.

In one embodiment the curing is performed in oxygen-depletedsurroundings. Without wanting to be bound by any particular theory, theapplicant believes that performing the curing in an oxygen-depletedsurrounding is particularly beneficial when the binder compositionincludes an enzyme because it increases the stability of the enzymecomponent in some embodiments, in particular of the transglutaminaseenzyme, and thereby improves the crosslinking efficiency. In oneembodiment, the curing process is therefore performed in an inertatmosphere, in particular in an atmosphere of an inert gas, likenitrogen.

In some embodiments, in particular in embodiments in which the bindercomposition includes phenolics, in particular tannins oxidizing agentscan be added. Oxidising agents as additives can serve to increase theoxidising rate of the phenolics in particular tannins. One example isthe enzyme tyrosinase which oxidizes phenols to hydroxy-phenols/quinonesand therefore accelerates the binder forming reaction.

In another embodiment, the oxidising agent is oxygen, which is suppliedto the binder.

In one embodiment, the curing is performed in oxygen-enrichedsurroundings.

EXAMPLES

In the following examples, several binders which fall under thedefinition used in the present disclosure were prepared and compared tobinders according to the prior art.

Test Methods for Binder Compositions According to the Prior Art

The following properties were determined for the binders according theprior art.

-   -   Reagents

Silane (Momentive VS-142) was supplied by Momentive and was calculatedas 100% for simplicity. All other components were supplied in highpurity by Sigma-Aldrich and were assumed anhydrous for simplicity unlessstated otherwise.

-   -   Binder Component Solids Content—Definition

The content of each of the components in a given binder solution beforecuring is based on the anhydrous mass of the components. The followingformula can be used:

${\text{Binder component solids content}\mspace{14mu}(\%)} = {\frac{\begin{matrix}{\text{binder component~~}\text{A}\text{solids (}\text{g}\text{) +}} \\{{\text{binder component~~}\text{B}\text{solids (}\text{g}\text{) +}}\cdots}\end{matrix}}{\text{total weight of mixture (}\text{g}\text{)}} \times 100\%}$

-   -   Binder Solids—Definition and Procedure

The content of binder after curing is termed “binder solids”.

Disc-shaped stone wool samples (diameter: 5 cm; height 1 cm) were cutout of stone wool and heat-treated at 580° C. for at least 30 minutes toremove all organics. The solids of the binder mixture (see below formixing examples) were measured by distributing a sample of the bindermixture (approx. 2 g) onto a heat treated stone wool disc in a tin foilcontainer. The weight of the tin foil container containing the stonewool disc was weighed before and directly after addition of the bindermixture. Two such binder mixture loaded stone wool discs in tin foilcontainers were produced and they were then heated at 200° C. for 1hour. After cooling and storing at room temperature for 10 minutes, thesamples were weighed and the binder solids were calculated as an averageof the two results. A binder with the desired binder solids could thenbe produced by diluting with the required amount of water and 10% aq.silane (Momentive VS-142).

-   -   Reaction Loss—Definition

The reaction loss is defined as the difference between the bindercomponent solids content and the binder solids.

-   -   Mechanical Strength Studies (Bar Tests)—Procedure

The mechanical strength of the binders was tested in a bar test. Foreach binder, 16 bars were manufactured from a mixture of the binder andstone wool shots from the stone wool spinning production. The shots areparticles which have the same melt composition as the stone wool fibers,and the shots are normally considered a waste product from the spinningprocess. The shots used for the bar composition have a size of 0.25-0.50mm.

A 15% binder solids binder solution containing 0.5% silane (MomentiveVS-142) of binder solids was obtained as described above under “bindersolids”. A sample of this binder solution (16.0 g) was mixed well withshots (80.0 g). The resulting mixture was then filled into four slots ina heat resistant silicone form for making small bars (4×5 slots perform; slot top dimension: length=5.6 cm, width=2.5 cm; slot bottomdimension: length=5.3 cm, width=2.2 cm; slot height=1.1 cm). Themixtures placed in the slots were then pressed hard with a suitablysized flat metal bar to generate even bar surfaces. 16 bars from eachbinder were made in this fashion. The resulting bars were then cured at200° C. for 1 h. After cooling to room temperature, the bars werecarefully taken out of the containers. Five of the bars were aged in awater bath at 80° C. for 3 h or in an autoclave (15 min/120° C./1.2bar).

After drying for 1-2 days, the aged bars as well as five unaged barswere broken in a 3 point bending test (test speed: 10.0 mm/min; rupturelevel: 50%; nominal strength: 30 N/mm2; support distance: 40 mm; maxdeflection 20 mm; nominal e-module 10000 N/mm2) on a Bent Tram machineto investigate their mechanical strengths. The bars were placed with the“top face” up (i.e. the face with the dimensions length=5.6 cm,width=2.5 cm) in the machine.

-   -   Loss of Ignition (LOI) of Bars

The loss of ignition (LOI) of bars was measured in small tin foilcontainers by treatment at 580° C. For each measurement, a tin foilcontainer was first heat-treated at 580° C. for 15 minutes to remove allorganics. The tin foil container was allowed to cool to ambienttemperature, and was then weighed. Four bars (usually after being brokenin the 3 point bending test) were placed into the tin foil container andthe ensemble was weighed. The tin foil container containing bars wasthen heat-treated at 580° C. for 30 minutes, allowed to cool to ambienttemperature, and finally weighed again. The LOI was then calculatedusing the following formula:

${{LOI}\mspace{14mu}(\%)} = {\frac{\begin{matrix}{{\text{Weight of bars before heat treatment (}\text{g}\text{)}} -} \\{\text{Weight of bars after heat treatment (}\text{g}\text{)}}\end{matrix}}{\text{Weight of bars before heat treatment (}\text{g}\text{)}} \times 100\%}$

-   -   Water Absorption Measurements

The water absorption of the binders was measured by weighing three barsand then submerging the bars in water (approx. 250 mL) in a beaker (565mL, bottom ∅=9.5 cm; top ∅=10.5 cm; height=7.5 cm) for 3 h or 24 h. Thebars were placed next to each other on the bottom of the beaker with the“top face” down (i.e. the face with the dimensions length=5.6 cm,width=2.5 cm). After the designated amount of time, the bars were liftedup one by one and allowed to drip off for one minute. The bars were held(gently) with the length side almost vertical so that the droplets woulddrip from a corner of the bar. The bars were then weighed and the waterabsorption was calculated using the following formula:

${{Waterabs}.(\%)} = {\frac{\begin{matrix}{{\text{Weight of bars after water treatment (}\text{g}\text{)}} -} \\{\text{Weight of bars before water treatment (}\text{g}\text{)}}\end{matrix}}{\text{Weight of bars before water treatment (}\text{g}\text{)}} \times 100\%}$

Reference Binder Compositions from the Prior Art

-   -   Binder Example, Reference Binder A (Phenol-Formaldehyde Resin        Modified with Urea, a PUF-Resol)

A phenol-formaldehyde resin is prepared by reacting 37% aq. formaldehyde(606 g) and phenol (189 g) in the presence of 46% aq. potassiumhydroxide (25.5 g) at a reaction temperature of 84° C. preceded by aheating rate of approximately 1° C. per minute. The reaction iscontinued at 84° C. until the acid tolerance of the resin is 4 and mostof the phenol is converted. Urea (241 g) is then added and the mixtureis cooled.

The acid tolerance (AT) expresses the number of times a given volume ofa binder can be diluted with acid without the mixture becoming cloudy(the binder precipitates). Sulfuric acid is used to determine the stopcriterion in a binder production and an acid tolerance lower than 4indicates the end of the binder reaction. To measure the AT, a titrantis produced from diluting 2.5 mL conc. sulfuric acid (>99%) with 1 L ionexchanged water. 5 mL of the binder to be investigated is then titratedat room temperature with this titrant while keeping the binder in motionby manually shaking it; if preferred, use a magnetic stirrer and amagnetic stick. Titration is continued until a slight cloud appears inthe binder, which does not disappear when the binder is shaken.

The acid tolerance (AT) is calculated by dividing the amount of acidused for the titration (mL) with the amount of sample (mL):AT=(Used titration volume (mL))/(Sample volume (mL))

Using the urea-modified phenol-formaldehyde resin obtained, a binder ismade by addition of 25% aq. ammonia (90 mL) and ammonium sulfate (13.2g) followed by water (1.3.0 kg). The binder solids were then measured asdescribed above and the mixture was diluted with the required amount ofwater and silane (Momentive VS-142) for mechanical strength studies (15%binder solids solution, 0.5% silane of binder solids).

Test Methods for Binder Compositions Used in to the Present Disclosureand Reference Binders

The following properties were determined for the binders used in thepresent disclosure and reference binders.

-   -   Reagents

Speisegelatines, type A, porcine (120 bloom and 180 bloom) were obtainedfrom Gelita AG. Tannorouge chestnut tree tannin was obtained fromBrouwland bvba. TI Transglutaminase formula was obtained from ModernistPantry. Coconut oil, hemp oil, olive oil, rapeseed oil and sunflower oilwere obtained from Urtekram International A/S. Linseed oil was obtainedfrom Borup Kemi I/S. Medium gel strength gelatin from porcine skin(170-195 g Bloom), sodium hydroxide, tung oil and all other componentswere obtained from Sigma-Aldrich. Unless stated otherwise, thesecomponents were assumed completely pure and anhydrous.

-   -   Binder Component Solids Content—Definition

The content of each of the components in a given binder solution beforecuring is based on the anhydrous mass of the components. The followingformula can be used:

${\text{Binder component solids content}\mspace{14mu}(\%)} = {\frac{\begin{matrix}{\text{binder component~~}\text{A}\text{solids (}\text{g}\text{) +}} \\{{\text{binder component~~}\text{B}\text{solids (}\text{g}\text{) +}}\cdots}\end{matrix}}{\text{total weight of mixture (}\text{g}\text{)}} \times 100\%}$

-   -   Mechanical Strength Studies (Bar Tests)—Procedure

The mechanical strength of the binders was tested in a bar test. Foreach binder, 16-20 bars were manufactured from a mixture of the binderand stone wool shots from the stone wool spinning production. The shotsare particles which have the same melt composition as the stone woolfibers, and the shots are normally considered a waste product from thespinning process. The shots used for the bar composition have a size of0.25-0.50 mm.

A binder solution with approx. 15% binder component solids was obtainedas described in the examples below. A sample of the binder solution(16.0 g) was mixed well with shots (80.0 g; pre-heated to 40° C. whenused in combination with comparatively fast setting binders). Theresulting mixture was then filled into four slots in a heat resistantsilicone form for making small bars (4×5 slots per form; slot topdimension: length=5.6 cm, width=2.5 cm; slot bottom dimension:length=5.3 cm, width=2.2 cm; slot height=1.1 cm). During the manufactureof each bar, the mixtures placed in the slots were pressed as requiredand then evened out with a plastic spatula to generate an even barsurface. 16-20 bars from each binder were made in this fashion. Theresulting bars were then cured at room temperature for 1-2 days. Thebars were then carefully taken out of the containers, turned upside downand left for a day at room temperature to cure completely. Five of thebars were aged in a water bath at 80° C. for 3 h or in an autoclave (15min/120° C./1.2 bar).

After drying for 1-2 days, the aged bars as well as five unaged barswere broken in a 3 point bending test (test speed: 10.0 mm/min; rupturelevel: 50%; nominal strength: 30 N/mm2; support distance: 40 mm; maxdeflection 20 mm; nominal e-module 10000 N/mm2) on a Bent Tram machineto investigate their mechanical strengths. The bars were placed with the“top face” up (i.e. the face with the dimensions length=5.6 cm,width=2.5 cm) in the machine.

-   -   Loss of Ignition (LOI) of Bars

The loss of ignition (LOI) of bars was measured in small tin foilcontainers by treatment at 580° C. For each measurement, a tin foilcontainer was first heat-treated at 580° C. for 15 minutes to remove allorganics. The tin foil container was allowed to cool to ambienttemperature, and was then weighed. Four bars (usually after being brokenin the 3 point bending test) were placed into the tin foil container andthe ensemble was weighed. The tin foil container containing bars wasthen heat-treated at 580° C. for 30 minutes, allowed to cool to ambienttemperature, and finally weighed again. The LOI was then calculatedusing the following formula:

${{LOI}\mspace{14mu}(\%)} = {\frac{\begin{matrix}{{\text{Weight of bars before heat treatment (}\text{g}\text{)}} -} \\{\text{Weight of bars after heat treatment (}\text{g}\text{)}}\end{matrix}}{\text{Weight of bars before heat treatment (}\text{g}\text{)}} \times 100\%}$

-   -   Water Absorption Measurements

The water absorption of the binders was measured by weighing three barsand then submerging the bars in water (approx. 250 mL) in a beaker (565mL, bottom ∅=9.5 cm; top ∅=10.5 cm; height=7.5 cm) for 3 h or 24 h. Thebars were placed next to each other on the bottom of the beaker with the“top face” down (i.e. the face with the dimensions length=5.6 cm,width=2.5 cm). After the designated amount of time, the bars were liftedup one by one and allowed to drip off for one minute. The bars were held(gently) with the length side almost vertical so that the droplets woulddrip from a corner of the bar. The bars were then weighed and the waterabsorption was calculated using the following formula:

${{Waterabs}.(\%)} = {\frac{\begin{matrix}{{\text{Weight of bars after water treatment (}\text{g}\text{)}} -} \\{\text{Weight of bars before water treatment (}\text{g}\text{)}}\end{matrix}}{\text{Weight of bars before water treatment (}\text{g}\text{)}} \times 100\%}$

Binder Compositions Used in the Present Disclosure and Reference Binders

-   -   Binder Example, Entry B

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 12.0g) in water (68.0 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.0). 1M NaOH (4.37 g) was then added(pH 9.1) followed by a portion of the above chestnut tree tanninsolution (5.40 g; thus efficiently 1.20 g chestnut tree tannin). Afterstirring for 1-2 minutes further at 50° C., the resulting brown mixture(pH 9.1) was used in the subsequent experiments.

-   -   Binder Example, Entry 3

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.1). 1M NaOH (4.00 g) was added (pH9.3) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Coconut oil(0.65 g) was then added under vigorous stirring. After stirringvigorously for approx. 1 minute at 50° C., the stirring speed was sloweddown again and the resulting brown mixture (pH 9.3) was used in thesubsequent experiments.

-   -   Binder Example, Entry 5

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 4.8). 1M NaOH (4.00 g) was added (pH9.2) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Linseed oil(0.65 g) was then added under vigorous stirring. After stirringvigorously for approx. 1 minute at 50° C., the stirring speed was sloweddown again and the resulting brown mixture (pH 9.2) was used in thesubsequent experiments.

-   -   Binder Example, Entry 6

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 4.8). 1M NaOH (4.00 g) was added (pH9.2) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Olive oil (0.65g) was then added under vigorous stirring. After stirring vigorously forapprox. 1 minute at 50° C., the stirring speed was slowed down again andthe resulting brown mixture (pH 9.1) was used in the subsequentexperiments.

-   -   Binder Example, Entry 9

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 4.8). 1M NaOH (4.00 g) was added (pH9.3) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Tung oil (0.16g) was then added under vigorous stirring. After stirring vigorously forapprox. 1 minute at 50° C., the stirring speed was slowed down again andthe resulting brown mixture (pH 9.4) was used in the subsequentexperiments.

-   -   Binder Example, Entry 11

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.0). 1M NaOH (4.00 g) was added (pH9.1) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Tung oil (1.13g) was then added under vigorous stirring. After stirring vigorously forapprox. 1 minute at 50° C., the stirring speed was slowed down again andthe resulting brown mixture (pH 9.1) was used in the subsequentexperiments.

-   -   Binder Example, Entry C

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 180 bloom, 12.0g) in water (68.0 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.0). 1M NaOH (3.81 g) was then added(pH 9.1) followed by a portion of the above chestnut tree tanninsolution (5.40 g; thus efficiently 1.20 g chestnut tree tannin). Afterstirring for 1-2 minutes further at 50° C., the resulting brown mixture(pH 9.3) was used in the subsequent experiments.

-   -   Binder Example, Entry 12

To 1M NaOH (15.75 g) stirred at room temperature was added chestnut treetannin (4.50 g). Stirring was continued at room temperature for 5-10 minfurther, yielding a deep red-brown solution.

A mixture of gelatin (Speisegelatine, type A, porcine, 180 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.0). 1M NaOH (3.28 g) was added (pH9.2) followed by a portion of the above chestnut tree tannin solution(4.50 g; thus efficiently 1.00 g chestnut tree tannin). Tung oil (0.65g) was then added under vigorous stirring. After stirring vigorously forapprox. 1 minute at 50° C., the stirring speed was slowed down again andthe resulting brown mixture (pH 9.1) was used in the subsequentexperiments.

-   -   Binder Example, Entry D

A mixture of gelatin (Porcine skin, medium gel strength, 12.0 g) inwater (62.0 g) was stirred at 37° C. for approx. 15-30 min until a clearsolution was obtained (pH 5.5). A solution of TI transglutaminase (0.60g) in water (6.0 g) was then added. After stirring for 1-2 minutesfurther at 37° C., the resulting tan mixture (pH 5.5) was used in thesubsequent experiments.

-   -   Binder Example, Entry 13

A mixture of gelatin (Porcine skin, medium gel strength, 12.0 g) inwater (62.0 g) was stirred at 37° C. for approx. 15-30 min until a clearsolution was obtained (pH 5.5). A solution of TI transglutaminase (0.60g) in water (6.0 g) was added. Linseed oil (0.63 g) was then added undermore vigorous stirring. After stirring more vigorously for approx. 1minute at 37° C., the stirring speed was slowed down again and theresulting tan mixture (pH 5.5) was used in the subsequent experiments.

-   -   Binder Example, Entry E

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 12.0g) in water (68.0 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 4.8). 1M NaOH (4.42 g) was then added.After stirring for 1-2 minutes further at 50° C., the resulting tanmixture (pH 9.0) was used in the subsequent experiments.

-   -   Binder Example, Entry 14

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.1). 1M NaOH (4.00 g) was added (pH9.4). Tung oil (0.65 g) was then added under vigorous stirring. Afterstirring vigorously for approx. 1 minute at 50° C., the stirring speedwas slowed down again and the resulting tan mixture (pH 9.1) was used inthe subsequent experiments.

-   -   Binder Example, Entry 15

A mixture of gelatin (Speisegelatine, type A, porcine, 120 bloom, 10.0g) in water (56.7 g) was stirred at 50° C. for approx. 15-30 min until aclear solution was obtained (pH 5.1). 1M NaOH (4.00 g) was added (pH9.3). Tung oil (1.13 g) was then added under vigorous stirring. Afterstirring vigorously for approx. 1 minute at 50° C., the stirring speedwas slowed down again and the resulting tan mixture (pH 9.1) was used inthe subsequent experiments.

TABLE 1-1 Reference binder according to the prior art Example A Binderproperties Binder solids (%) 15.0 Reaction loss (%) 28.5 pH 9.6 Barcuring conditions Temperature (° C./1 h) 200 Bar properties Mechanicalstrength, unaged (kN) 0.39 Mechanical strength, water bath aged (kN)0.28 Mechanical strength, autoclave aged (kN) 0.28 LOI, unaged (%) 2.8LOI, water bath aged (%) 2.8 Water absorption, 3 h (%) 4 Waterabsorption, 24 h (%) 8

TABLE 1-2 Hydrocolloid, crosslinker, mineral oil or fatty acid ester ofglycerol Example B 1 2 3 4 5 6 Binder composition Hydrocolloid (%-wt.)Gelatin, Speisegelatine, 120 100 100 100 100 100 100 100 bloom Gelatin,Speisegelatine, 180 — — — — — — — bloom Crosslinker (%-wt.) ^([a])Chestnut tree tannin 10 10 10 10 10 10 10 Fatty acid ester of glycerol(%-wt.) ^([a]) Mineral oil — 1.6 6.5 — — — — Coconut oil (iodine — — —6.5 — — — number 7 to 10) Hemp oil (iodine — — — — 6.5 — — number 140 to170) Linseed oil (iodine — — — — — 6.5 — number 136 to 178) Olive oil(iodine — — — — — — 6.5 number 80 to 88) Base (%-wt.) ^([b]) Sodiumhydroxide 2.5 2.6 2.5 2.5 2.5 2.5 2.5 Binder mixing and bar manufactureBinder component solids 15.1 15.2 15.7 15.7 15.7 15.7 15.7 content (%)pH of binder mixture 9.1 9.1 9.1 9.3 9.1 9.2 9.1 Curing temperature (°C.) rt rt rt rt rt rt rt Bar properties Mechanical strength, 0.22 0.190.18 0.31 0.31 0.34 0.34 unaged (kN) Mechanical strength, 0.17 0.12 0.120.25 0.24 0.30 0.28 aged (kN) LOI, unaged (%) 2.9 2.9 2.9 3.0 3.0 3.03.0 LOI, water bath aged (%) 2.6 2.6 2.7 2.8 2.8 2.8 2.8 Waterabsorption, 3 h (%) 16 18 16 10 10 9 10 Water absorption, 24 h (%) 31 3132 23 24 23 22 ^([a]) Of hydrocolloid. ^([b]) Of hydrocolloid +crosslinker.

TABLE 1-3 Hydrocolloid, crosslinker, fatty acid ester of glycerolExample B 7 8 9 10 11 C 12 Binder composition Hydrocolloid (%-wt.)Gelatin, Speisegelatine, 100 100 100 100 100 100 — — 120 bloom Gelatin,Speisegelatine, — — — — — — 100 100 180 bloom Crosslinker (%-wt.) ^([a])Chestnut tree tannin 10 10 10 10 10 10 10 10 Fatty acid ester ofglycerol (%-wt.) ^([a]) Rapeseed oil (iodine — 6.5 — — — — — — number 94to 120) Sunflower oil (iodine — — 6.5 — — — — — number 118 to 144) Tungoil (iodine — — — 1.6 6.5 11.3 — 6.5 number 163 to 173) Base (%-wt.)^([b]) Sodium hydroxide 2.5 2.5 2.5 2.6 2.5 2.4 2.3 2.2 Binder mixingand bar manufacture Binder component solids 15.1 15.7 15.7 15.2 15.716.3 15.1 15.9 content (%) pH of binder mixture 9.1 9.1 9.2 9.4 9.1 9.19.3 9.1 Curing temperature (° C.) rt rt rt rt rt rt rt rt Bar propertiesMechanical strength, 0.22 0.28 0.26 0.29 0.32 0.28 0.24 0.37 unaged (kN)Mechanical strength, 0.17 0.25 0.21 0.22 0.22 0.21 0.17 0.34 aged (kN)LOI, unaged (%). 2.9 2.9 3.0 2.9 3.0 3.1 2.9 3.0 LOI, water bath aged(%) 2.6 2.8 2.8 2.7 2.9 3.0 2.8 2.9 Water absorption, 3 h (%) 16 11 1011 8 8 13 9 Water absorption, 24 h (%) 31 25 24 24 23 20 25 22 ^([a]) Ofhydrocolloid. ^([b]) Of hydrocolloid + crosslinker.

TABLE 1-4 Hydrocolloid, crosslinker, fatty acid ester of glycerolExample D 13 E 14 15 Binder composition Hydrocolloid (%-wt.) Gelatin(porcine skin), 100 100 — — — medium gel strength Gelatin,Speisegelatine, — — 100 100 100 120 bloom Crosslinker (%-wt.) ^([a]) TItransglutaminase 5 5 — — — Fatty acid ester of glycerol (%-wt.) ^([a])Tung oil (iodine number — — — 6.5 11.3 163 to 173) Linseed oil (iodine —5.3 — — — number 136 to 178) Base (%-wt.) ^([b]) Sodium hydroxide — —1.4 1.5 1.5 Binder mixing and bar manufacture Binder component 15.6 16.314.4 15.1 15.7 solids content (%) pH of binder mixture 5.5 5.5 9.0 9.19.0 Curing temperature rt rt rt rt rt (° C.) Bar properties Mechanicalstrength, 0.28 0.29 0.16 0.22 0.19 unaged (kN) Mechanical strength, 0.200.20 — — — water bath aged (kN) Mechanical strength, — — 0.16 0.28 0.24autoclave aged (kN) LOI, unaged (%) 3.0 3.2 2.7 3.0 3.1 LOI, water bathaged (%) 2.7 2.8 — — — Water absorption, 6 5 — — — 3 h (%) Waterabsorption, 9 10 — — — 24 h (%) ^([a]) Of hydrocolloid. ^([b]) Ofhydrocolloid + crosslinker.

As shown in the FIGS. 1 to 3 a web 1 of mineral wool material comprisingan uncured binder is placed between two moulding parts 2, 3. The web 1is then pressed into the shape as the first moulding part 2 having apositive form 21 is biased towards the second moulding part 3 having acavity 31.

The mineral wool material 1′ in the mould is then cured while being heldbetween the moulding parts 2, 3. The curing may be achieved by applyinga slightly elevated temperature, e.g. by blowing warm air through theweb 1 via openings in the moulding parts 2, 3 (not shown) or by applyinga vacuum to the mould which causes the binder to dry and thereby achieveits final cured stage. Since the temperature required is relatively low,e.g. between 20 to 60° C., such as 40 to 50° C., the moulding parts 2, 3can be made in a wide range of materials making the moulding partsrelatively inexpensive to produce.

After the mineral wool material in the mould is cured the moulding parts2, 3 are taken apart and the finished mould product 10 is freed from themould and ready for further processing.

As schematically shown in FIGS. 4 and 5 , insulating pipe sections maybe moulded by winding a mineral wool web 1 around a mandrel 4. The web 1may be provided with a cured binder and extra binder may be sprayed ontothe surface by a spraying device 5. This additional binder then acts asan adhesive so that several layers of material may be wound onto themandrel 4 for forming a pipe section with a predetermined wallthickness. The outer surface of the pipe section is preferably supportedby rollers, a belt or even a closed moulding part (not shown). Theresulting pipe section product 10 may then be subjected to adrying/curing process preferably with a slightly increased temperatureso that the binder adhesive is cured. In another embodiment, the mineralwool web is initially uncured and then the entire cylinder may be curedbefore being removed from the mandrel. In this embodiment it is normallynot necessary to add any additional binder during the winding process.

With reference to FIG. 6 , an insulating pipe section may be formedusing a core rod 6 and then folding an uncured mineral wool web 1 aroundit and then cure the binder. Also in this embodiment there is oftenprovided a moulding part that supports the outer surface of the foldedmineral wool web 1 (not shown). This method of moulding or forming apipe section allows for producing tubular products 10 with a longlength.

Many other types of mineral wool products than those already mentionedmay be produced in accordance with the disclosure. Examples are apre-shaped insulation part, such as for a valve, a pipe bend or thelike; a pre-shaped insulation part for a vehicle; a pre-shaped growthsubstance block or plug or slab; a pre-shaped ceiling tile; or apre-shaped water management product for storing or transferring water.

The mould used in the disclosure may be provided with means for blowingair through the mineral wool web for curing the binder. Alternatively,the mould may be sealed when it is closed and a vacuum may then beprovided for drying the binder, whereby it achieves its final curedstage.

The invention claimed is:
 1. A method of producing a moulded mineralwool product, said method comprising: providing a mixture by mixingmineral fibres with a binder composition comprising at least onehydrocolloid and at least one crosslinker, wherein the at least onehydrocolloid comprises a protein; providing said mixture in a mouldform; curing the binder composition; and removing the moulded mineralwool product from the mould form.
 2. The method according to claim 1,wherein the binder composition further comprises at least one fatty acidester of glycerol.
 3. The method according claim 2, wherein the at leastone fatty acid ester of glycerol is in form of a plant oil and/or animaloil.
 4. The method according to claim 2, wherein the at least one fattyacid ester of glycerol is a plant-based oil.
 5. The method according toclaim 2, wherein the at least one fatty acid ester of glycerol isselected from one or more components from the group consisting linseedoil, olive oil, tung oil, coconut oil, hemp oil, rapeseed oil, andsunflower oil.
 6. The method according to claim 2, wherein the at leastone fatty acid ester of glycerol is in form of an animal oil, such asfish oil.
 7. The method according to claim 2, wherein the at least onefatty acid ester of glycerol comprises a plant oil and/or animal oilhaving a iodine number of ≥75.
 8. The method according to claim 2,wherein the at least one fatty acid ester of glycerol comprises a plantoil and/or animal oil having an iodine number of ≤100.
 9. The methodaccording to claim 2, wherein the content of the fatty acid ester ofglycerol is 0.5 to 40 wt.-%, based on dry hydrocolloid basis.
 10. Themethod according to claim 1, wherein the mould form comprises a firstmoulding part having a first moulding shape and a second moulding parthaving a second moulding shape, said first moulding part and said secondmoulding part being closed around the mixture.
 11. The method accordingto claim 10, further comprising compressing the mixture in the mouldform between the first moulding part and the second moulding part. 12.The method according to claim 11, wherein the mixture is formed into aweb, which is then provided into the mould form.
 13. A method ofproducing a tubular mineral wool insulation product, said methodcomprising: producing a web comprising a mixture of mineral fibres and abinder composition comprising at least one hydrocolloid and at least onecrosslinker, wherein the at least one hydrocolloid comprises a protein;applying said web around a core; curing the binder composition; andremoving the tubular mineral wool insulation product from the core. 14.The method according to claim 13, wherein the binder composition furthercomprises at least one fatty acid ester of glycerol.
 15. The methodaccording claim 14, wherein the at least one fatty acid ester ofglycerol is in form of a plant oil and/or animal oil.
 16. The methodaccording to claim 14, wherein the at least one fatty acid ester ofglycerol is a plant-based oil.
 17. The method according to claim 14,wherein the at least one fatty acid ester of glycerol is selected fromone or more components from the group consisting linseed oil, olive oil,tung oil, coconut oil, hemp oil, rapeseed oil, and sunflower oil. 18.The method according to claim 14, wherein the at least one fatty acidester of glycerol is in form of an animal oil, such as fish oil.
 19. Themethod according to claim 14, wherein the at least one fatty acid esterof glycerol comprises a plant oil and/or animal oil having a iodinenumber of ≥75.
 20. The method according to claim 14, wherein the atleast one fatty acid ester of glycerol comprises a plant oil and/oranimal oil having a iodine number of ≤100.
 21. The method according toclaim 14, wherein the content of the fatty acid ester of glycerol is 0.5to 40 wt.-%, based on dry hydrocolloid basis.
 22. The method accordingto claim 13, wherein the application of the web around a core is done bywinding said web around a core mandrel.
 23. The method according toclaim 13, wherein the binder composition in the mixture is uncuredbefore the web is applied around the core.
 24. The method according toclaim 22, wherein the binder composition in the mixture is cured beforewinding the web around the core mandrel, and wherein a further bindercomposition comprising at least one hydrocolloid is applied to the web,e.g. by spraying, during the winding of the web around the core mandrel.25. The method according to claim 13, further comprising cutting theends of the tubular mineral wool insulation product to provide theproduct in a predetermined length.
 26. The method according to claim 13,further comprising applying a metal foil around the tubular mineral woolinsulation product.
 27. The method according to claim 13, wherein the atleast one hydrocolloid comprises gelatin.
 28. The method according toclaim 13, wherein the at least one hydrocolloid is a polyelectrolytichydrocolloid.
 29. The method according to claim 28, wherein the at leastone hydrocolloid comprises gelatin.
 30. The method according to claim13, wherein the binder composition comprises at least two hydrocolloids,wherein one of the at least two hydrocolloids is gelatin and another oneof the at least two hydrocolloids is selected from the group consistingof pectin, starch, alginate, agar agar, carrageenan, gellan gum, guargum, gum arabic, locust bean gum, xanthan gum, cellulose derivativessuch as carboxymethylcellulose, arabinoxylan, cellulose, curdlan,β-glucan.
 31. The method according to claim 30, wherein the gelatin ispresent in the binder by an amount of 10 to 95 wt. % based on the weightof the hydrocolloids.
 32. The method according to claim 30, wherein theone of the at least two hydrocolloids and the another one of the atleast two hydrocolloids have complementary charges.
 33. The methodaccording to claim 13, wherein curing the binder composition takes placeat a temperature of not more than 95° C.
 34. The method according toclaim 13, wherein the binder composition is not a thermoset binder. 35.The method according to claim 13, wherein the binder composition doesnot contain a poly(meth)acrylic acid, a salt of a poly(meth)acrylic acidor an ester of a poly(meth)acrylic acid.
 36. The method according toclaim 13, wherein the at least one hydrocolloid is a biopolymer ormodified biopolymer.
 37. The method according to claim 13, wherein thebinder composition is formaldehyde-free.
 38. The method according toclaim 30, wherein the binder composition consists essentially of: the atleast two hydrocolloids; the at least one fatty acid ester of glycerol;the at least one crosslinker; optionally at least one pH-adjuster;optionally at least one anti-fouling agent; optionally at least oneanti-swelling agent; and water.
 39. The method according to claim 30,wherein the method involves crosslinking the protein of the bindercomposition.
 40. The method according to claim 30, wherein curing thebinder composition comprises blowing air or gas over/through the mineralwool product or increasing temperature.
 41. The method according toclaim 1, wherein curing the binder composition comprises application ofa vacuum.
 42. The method according to claim 1, wherein the at least onecrosslinker comprises at least one phenol containing compound, at leastone quinone containing compound, or both.
 43. The method according toclaim 42, wherein the at least one crosslinker comprises a tannin or anenzyme.